Liver samples from 53 Franciscana dolphins along the Brazilian coast were analyzed for organobrominated compounds. Target substances included the following anthropogenic pollutants: polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), decabromodiphenylethane (DBDPE), as well as the naturally-generated methoxylated-PBDEs (MeO-PBDEs). PBDE concentrations ranged from 6 to 1797 ng/g lw (mean 166 ± 298 ng/g lw) and were similar to those observed in cetaceans from Northern Hemisphere. PBBs were found in all sampling locations (<LOQ to 57 ng/g lw). DBDPE was detected in 42% of the dolphins from the most industrialized Brazilian state and the concentrations ranging from <LOQ to 352 ng/g lw. Franciscana dolphins from the tropical Brazilian shore presented the highest MeO-PBDE concentrations ever reported for coastal cetaceans (up to 14 μg/g lw). Eight MeO-PBDE congeners were detected and the present investigation constituted the first record of occurrence of six of them in marine mammal livers. ► PBDE, emerging BFR and MeO-PBDE levels in Franciscana dolphin from Brazil were reported. ► Six MeO-PBDEs were detected for the first time in marine mammals. ► PBDE contamination was similar than those from other industrialized areas around the world. ► MeO-PBDEs presented the higher concentrations found in coastal biota worldwide. Concentrations and accumulation profiles of PBDEs, MeO-PBDEs and emerging brominated compounds in livers of dolphins from South Atlantic.